Catalytic Routes For The Conversion of Biomass Into Liquid Hydrocarbon

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Environmental Science
Cite this: Energy Environ. Sci., 2011, 4, 83
www.rsc.org/ees PERSPECTIVE
Catalytic routes for the conversion of biomass into liquid hydrocarbon
transportation fuels
Juan Carlos Serrano-Ruiz*a and James A. Dumesicb
Received 13th September 2010, Accepted 26th October 2010
Published on 30 November 2010 on http://pubs.rsc.org | doi:10.1039/C0EE00436G
DOI: 10.1039/c0ee00436g
Concerns about diminishing fossil fuel reserves along with global warming effects caused by increasing
levels of CO2 in the atmosphere are driving society toward the search for new renewable sources of energy
that can substitute for coal, natural gas and petroleum in the current energy system. Lignocellulosic
biomass is abundant, and it has the potential to significantly displace petroleum in the production of fuels
for the transportation sector. Ethanol, the main biomass-derived fuel used today, has benefited from
production by a well-established technology and by partial compatibility with the current transportation
infrastructure, leading to the domination of the world biofuel market. However, ethanol suffers from
Downloaded on 13 September 2012
important limitations as a fuel (e.g., low energy density, high solubility in water) than can be overcome by
designing strategies to convert non-edible lignocellulosic biomass into liquid hydrocarbon fuels (LHF)
chemically similar to those currently used in internal combustion engines. The present review describes
the main routes available to carry out such deep chemical transformation (e.g., gasification, pyrolysis,
and aqueous-phase catalytic processing), with particular emphasis on those pathways involving
aqueous-phase catalytic reactions. These latter catalytic routes achieve the required transformations in
biomass-derived molecules with controlled chemistry and high yields, but require pretreatment/
hydrolysis steps to overcome the recalcitrance of lignocellulose. To be economically viable, these
aqueous-phase routes should be carried out with a small number of reactors and with minimum
utilization of external fossil fuel-based hydrogen sources, as illustrated in the examples presented here.
1. Introduction millions of years to be formed, and they are currently being

consumed at a rate that is orders of magnitude higher than their
Society has reached high levels of development during the last natural regeneration cycle, making them non-renewable sources
century. This progress, however, has been achieved at the of energy. The most recent data available for world energy
expense of extensive consumption of natural resources, such as consumption indicate that society still remains highly dependent
petroleum, natural gas and coal. These fossil fuel resources took on fossil fuels at the present time. For example in 2008, fossil
fuels supplied 85% of the total energy consumed in the US,1 and
a
Advanced Materials Laboratory, Department of Inorganic Chemistry, almost 80% of the energy produced in the European Union.2
University of Alicante, Apartado 99, 03080 Alicante, Spain. E-mail: These fossil fuel resources are used to provide energy for various
jcserrano@ua.es; Fax: +34 965 903 454; Tel: +34 965 903 400 ext. 2048
b sectors of society (i.e., residential, commercial, industrial,
Department of Chemical and Biological Engineering, University of
Wisconsin–Madison, WI, 53706, USA. E-mail: dumesic@engr.wisc.edu; transportation and electrical power), among which the trans-
Fax: +1 608 262 5434; Tel: +1 608 262 1095 portation sector is the largest and fastest growing energy sector,
Broader context
The production of liquid transportation fuels from renewable biomass sources is a promising route that can help to decrease our
dependence on petroleum and to mitigate environmental issues. The transportation sector of our society and its entire infrastructure
is based on petroleum-derived liquid hydrocarbons, the latter of which possess high energy density and optimum combustion
characteristics. First-generation biofuels (i.e., ethanol and biodiesel) are produced from food crops, and present different chemical
compositions than conventional hydrocarbon fuels, creating important compatibility and energy density issues. One promising
alternative to overcome these limitations of oxygenated fuels is to use non-edible biomass (i.e., lignocellulose) to produce liquid
hydrocarbon fuels chemically similar to those currently used in cars, trucks or aircraft. The present paper describes the most
promising routes to achieve this transformation, with special emphasis on those approaches involving catalytic reactions.
This journal is ª The Royal Society of Chemistry 2011 Energy Environ. Sci., 2011, 4, 83–99 | 83
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responsible for almost one third of the total energy consumed in Fossil fuels reserves are not equally distributed around the
the world. Moreover, a large fraction of the energy for the world. The Middle-East countries control the 60% of the oil
transportation sector (96%) is currently derived from petroleum.3 reserves and the 41% of natural gas supplies, and only three
Three important issues are associated with the large-scale countries (US, China and Russia) account for 60% of the world
utilization of fossil fuels: availability, global warming and uneven recoverable coal reserves.4 This situation can lead to economic
geographic distribution of reserves. Fossil fuels are finite and, as instabilities, requires the transportation of fossil fuel resources
indicated above, their current consumption rate is higher than over long distances, and can cause political and security prob-
their corresponding regeneration rate, leading inevitably to lems worldwide.
depletion. Projections for the near future indicate that world The issues outlined above, inherently associated with fossil
energy consumption will increase by 35% over the next 20 years fuels, suggest that society requires new sources of energy to
to meet the growing demand of industrialized countries and the ensure progress and protect the environment for future genera-
rapid development of emerging economies,4 and world demand tions. These new sources of energy should: (i) have the potential
for petroleum will raise by 30%, reaching 111 millions of barrels to effectively replace fossil fuels in the current energy production
per day in 2035.5 Taking into account these forecasts and current system and (ii) be renewable, well distributed around the world,
data of proven reserves, it has been estimated that oil, natural gas and not contribute to the accumulation of greenhouse gases into
and coal will be depleted within the next 40, 60 and 120 years, the atmosphere. In this respect, natural resources such as solar
respectively.6 In the case of petroleum, many researchers predict energy, wind, hydroelectric power, geothermal activity, and
a more dramatic situation and estimate that the global produc- biomass meet these requirements. Unlike fossil fuels, they are
tion of oil will reach a maximum in the year 2020 and decay abundant and allow the development of zero-carbon or carbon-
thereafter.7 neutral technologies, thus contributing to mitigation of global
Global warming is, possibly, the most dramatic and known warming effects. Substitution of fossil fuel-based technologies
collateral effect produced by the massive utilization of fossil for those derived from renewable sources is currently spurred by
fuels.8 Fossil fuels are transformed into energy by means of various governments,9,10 and it will be done progressively and
combustion reactions, leading to net emissions of CO2, a strong selectively. Thus, while solar, wind, hydroelectric, and
greenhouse gas, into the atmosphere. Accordingly, the extraction geothermal have been proposed as excellent alternatives to coal
of fossil fuels for energy production has allowed a large part of and natural gas for heat and electricity production in stationary
the carbon stored in the earth for millions of years to be released power applications,11,12 biomass is the only sustainable source of
in just a few decades. organic carbon currently available on earth,13 and it is considered
Dr Juan Carlos Serrano-Ruiz James A. Dumesic earned his

studied Chemistry at the BS degree from UW–Madison
University of Granada (Spain). and his MS and PhD degrees
In 2001 he moved to the from Stanford University, under
University of Alicante (Spain) the supervision of Professor
where he received a PhD in Michel Boudart. Dumesic joined
Chemistry and Materials the Department of Chemical
Science in 2006 under the Engineering in 1976, and he is
supervision of Prof. Francisco currently the Steenbock Chair in
Rodrıguez-Reinoso and Antonio the College of Engineering. He
Sepulveda-Escribano. In has recently studied how
January 2008 he was awarded aqueous-phase reforming of
a Fulbright fellowship to glucose or sorbitol can be
Juan Carlos Serrano-Ruiz conduct studies on biomass James A: Dumesic tailored to selectively produce
conversion to fuels and chem- H2 or directed to produce
icals by catalytic approaches in hexane. He has investigated
Prof. James Dumesic’s research group at the University of Wis- methods to produce liquid alkanes by acid catalyzed dehydration of
consin–Madison, Madison (USA). In January 2010 he joined the sugars, followed by aldol-condensation over solid base catalysts.
Advanced Materials Laboratory (LMA) at the University of He has shown how that liquid alkanes can be produced from
Alicante where he has initiated a new research line on catalytic glycerol via an integrated process involving catalytic conversion to
routes for the conversion of biomass into liquid hydrocarbon fuels. H2/CO gas mixtures and Fischer–Tropsch synthesis in a single
He is member of the Spanish Biomass Technology Platform reactor, and he has studied strategies for catalytic conversion of
(BioPlat) and he belongs to the Spanish Biofuels for Transport sugars and polyols to hydrocarbons by first producing monofunc-
Working Group. tional intermediates over PtRe/C catalysts, followed by catalytic
upgrading to control the extent of C–C coupling. Most recently, he
has been studying the use of levulinic acid and g-valerolactone as
biomass-derived platform chemicals for the production of fuels and
chemicals.
84 | Energy Environ. Sci., 2011, 4, 83–99 This journal is ª The Royal Society of Chemistry 2011
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to be an ideal substitute for petroleum in the production of fuels, a renewable fuel in existing spark-ignition engines. This
chemicals and carbon-based materials.14,15 However, when compatibility, however, is not complete and the use of ethanol is
designing strategies for potential replacement of crude oil by presently limited to low-concentration blends (5–10% by
biomass, it is important to note that the petrochemical industry volume), namely E5–E10. Ethanol-enriched mixtures such as
currently consumes three quarters of the crude oil to cover the E85 require cars with specially designed engines, designated as
demand for liquid hydrocarbon fuels of the transportation flexible-fuel vehicles (FFVs), which are commonly used only in
sector, whereas only a small fraction of the petroleum is utilized a few countries like Brazil and Sweden. E85 mixtures are not
in the synthesis of industrial chemicals and other derivatives.16 tolerated by conventional vehicles, because ethanol, especially in
Consequently, an effective implementation of biomass in the high-concentration blends, can cause corrosion of some metallic
current energy system will necessarily involve the development of components in tanks and deterioration of rubbers and plastics
new technologies for the large-scale production of biofuels. used in internal combustion engines.21 This constraint in ethanol
At the present time, two biomass-derived fuels (so-called first blending represents the main issue of the growing ethanol
generation of biofuels) have been successfully implemented in the industry. As outlined in Fig. 1, projections indicate that the US
transportation sector: biodiesel (a mixture of long-chain alkyl ethanol industry will approach the blending wall (i.e., the point at
esters produced by transesterification of vegetable oils with which blending 10% of ethanol in each gallon of gasoline will not
methanol) and ethanol (produced by bacterial fermentation of be able to accommodate the rate of ethanol production) in
corn and sugar cane-derived sugars). The penetration of these 2010.22 Furthermore, experts predict that the number of E85
liquid biofuels in the transportation sector is still very weak, and fuelling stations and flexi-fuel vehicles will not grow sufficiently
in 2005 they represented only 2% of the total transportation fast to accommodate the growing volumes of ethanol produced
energy.3 However, the important environmental and economic in the US.23 A potential solution to overcome the blending wall is
benefits derived from their large-scale utilization will stimulate to raise the amount the ethanol allowed in gasoline to beyond
society to progressively increase reliance on biofuels. Thus, 10% by commercializing intermediate ethanol blends (i.e., E15–
according to projections by the International Energy Agency, the E20) (Fig. 1). However, there are serious issues in using blends
world biofuel production will increase from the current level of with higher ethanol concentrations. In countries like the US, the
1.9 million of barrels per day (mbd) in 2010 to 5.9 mbd by 2030, utilization of E15–E20 blends in regular vehicles is still not
which represents 6.3% of the world conventional fuels produc- authorized, since the effect of these mixtures on pollutant emis-
tion.4 Unlike petroleum-based fuels, liquid biofuels are consid- sions, driving performance and materials compatibility (e.g.,
ered carbon neutral since CO2 produced during fuel combustion tanks, pipelines, dispensers) is not fully understood,23 and
is consumed by subsequent biomass regrowth.17 Furthermore, current European standards allow only for E5 blends.18
recent studies indicate that the use of liquid biofuels produced Apart from the aforementioned blending issues, ethanol
domestically would strengthen economies by reducing the presents another important limitation as a transportation fuel.
dependence of foreign oil and by creating new well-paid jobs in Ethanol contains less energy per volume (i.e., energy density)
different sectors such as agricultural, forest management and oil than conventional gasoline, which ultimately reduces the fuel
industries.18 mileage of the vehicles. In this sense, it has been estimated that
cars running on ethanol rich mixtures like E85 operate with 30%
2. Lignocellulosic liquid hydrocarbon fuels: lower fuel mileage.24 This fact, along with the small price
differential between E85 and regular gasoline, has discouraged
alternative to ethanol
drivers to purchase E85 cars or fuel so far.22
The current biofuel market is largely dominated by ethanol,
which accounts for 90% of world biofuel production.19 Indeed,
the rate of ethanol production around the world is increasing
rapidly, from 13 billion gallons in 2007 to the current level of
almost 20 billion gallons in 2009,20 with the US (55%, corn-
derived) and Brazil (33%, sugar cane-derived) being the main
producers.21 The ethanol industry has benefited from a mature
and simple technology in which selected microorganisms (e.g.,
yeast, bacteria, and mold) transform aqueous sugars to the
desired final ethanol product. Ethanol is added to gasoline to
increase the octane number of the mixture and, with it, improve
the combustion characteristics of the fuel. The oxygen in ethanol
allows low-temperature combustion with the subsequent reduc-
tion of pollutants such as CO and NOx.19 Additionally, apart
from CO2 emission savings, blending gasoline with ethanol helps
Fig. 1 Volumes of ethanol absorbed by several blends in the US. Target
to reduce SOx emissions to the atmosphere, because ethanol
for biofuels production refers to the level of biofuels production
contains a negligible amount of sulfur compared to petroleum.18 mandated by the Energy Independence Security Act of 2007 (EISA
A key aspect that is responsible for expansion of the ethanol 2007).26 Maximum consumption for a determined blend refers to the
industry in recent years is the compatibility of ethanol with the ethanol consumed if all the gasoline used in the country is blended with
existing infrastructure for gasoline. Thus, ethanol blended with ethanol in the amount indicated. Source: Biomass Research and Devel-
conventional gasoline is currently used in many countries as opment Board.23
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Conventional transportation fuels are composed of liquid

hydrocarbons with different molecular weights (e.g., C5–C12 for
gasoline, C9–C16 for jet fuel, and C10–C20 for diesel applications)
and chemical structures (e.g., branched for gasoline, linear for
diesel). The entire transportation infrastructure (including
engines, fueling stations, distribution networks, and storage
tanks) has been developed to take advantage of the excellent
properties of these compounds as fuels. Thus, the special
composition of hydrocarbons fuels, based only on carbon and
hydrogen, provides them with high energy-density and stability
(allowing efficient storage at ambient conditions) and superior
combustion characteristics, properties highly desired for trans-
portation liquids. Thus, instead of using biomass to produce

oxygenated fuels (such as ethanol) with new compositions, an
attractive alternative would be to utilize biomass to generate
liquid fuels chemically similar to those being used today derived
from oil.17,25 These new fuels would be denoted as green gasoline,
Fig. 2 Water tolerance of some gasoline–ethanol blends as a function of
green diesel and green jet fuel, and they would be essentially the
temperature. Adapted from ref. 27.
same as those currently used in the transportation fleet, except
that they would be synthesized from biomass instead of petro-
leum. When compared with ethanol, the production of hydro- water when temperature decreases), or even from the ethanol
carbon fuels from biomass has important advantages. The main itself which typically carries traces of water when delivered from
benefit would include full compatibility with the existing energy the biorefinery. In this respect, many countries have regulated the
system. Since green hydrocarbon fuels would be essentially the maximum amount of water allowed in fuel-grade ethanol to the
same as those currently obtained from petroleum, it would not be level of 1% (v/v), to avoid phase separation issues.28 Ethanol
necessary to modify engines, pumps or distribution networks to affinity for water has important implications for distribution
accommodate the new renewable liquids in the transportation logistics as well. Pipelines, considered to be the least expensive
sector. means of safely transporting bulk fuel shipments,23 are not suited
Unlike ethanol, biomass-based hydrocarbons fuels are energy to transport ethanol or gasoline–ethanol blends on a commercial
equivalent to fuels derived from petroleum. The heating value scale, because apart from corrosion issues, ethanol can pick up
(i.e., the heat released when a known quantity of fuel is burned water in the pipeline with the potential result of phase-separa-
under specific conditions) of ethanol is only two-thirds that of tion. Consequently, ethanol has to be distributed by other fossil
gasoline, which, as indicated above, penalizes the fuel mileage fuel-consuming transportation modes such as rail, truck and
of the vehicles running on gasoline–ethanol mixtures. The use of barge. The hydrophobic character of biomass-derived hydro-
renewable hydrocarbon fuels would additionally help to meet the carbons eliminates these problems, since these molecules are
increased standards of fuel economy imposed by governments to immiscible in water. Additionally, the ability of liquid hydro-
the automobile industry. In the case of the US, these standards carbons to self-separate from water, as represented in Fig. 3, is
establish a mandatory increase in average fuel economy from the highly beneficial in that it eliminates the need for expensive and
current 25 miles per gallon (mpg) to 35 mpg by 2022.26 energy-consuming distillation steps required in the ethanol
The addition of oxygenated components to conventional fuels purification process. In particular, ethanol is initially obtained in
increases the water solubility of the mixture. This increase is
particularly marked in the case of gasoline–ethanol blends, since
pure ethanol is highly hygroscopic and completely miscible in
water. Thus, adding 10% of ethanol to regular gasoline raises the
water solubility of the blend more than 30 times (from 150 ppm
v/v of regular gasoline to 5000 ppm for E10).27 Once the water
contamination reaches the saturation level, additional water
separates from the mixture, removing the ethanol from gasoline
and leading to phase separation. In fact, when phase separation
occurs in the storage tank, the ethanol–water layer may combust
in the engine at higher temperatures causing damage to it.27 The
water tolerance of a gasoline–ethanol blend (i.e., fraction of
water that the mixture can contain without phase separation)
decreases with temperature and increases with ethanol content
(Fig. 2). Consequently, phase separation is an important concern
in countries with cooler climates and when low-concentration Fig. 3 Picture showing spontaneous separation between aqueous phase
blends such as E5 are used. Water can be absorbed by the and liquid alkanes produced by processing of biomass-derived molecules
ethanol–gasoline mixture from the atmosphere (in the form of in a four-phase flow reactor. Source: Dumesic’s Research Group web site,
moisture), from the air trapped in the tank (by condensation of http://jamesadumesic.che.wisc.edu/index2.htm.
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form of a dilute aqueous solution (5–12% v/v), which is subse- increase for this resource.35 Thus, according to recent analyses,
quently concentrated to 96–99% by distillation. It is estimated the cost of producing lignocellulosic ethanol would be almost
that this intense water removal step is responsible for 35–40% of double that of corn-derived ethanol.19 This fact represents the
the total energy required for ethanol production,29 and this main limitation of lignocellulose as a renewable resource, and the
energy is typically supplied by combustion of fossil fuels such as lack of cost-competitive technologies for the generation of liquid
natural gas. fuels from non-edible sources has been identified by experts as
Any technology envisaged to convert biomass feedstocks into the key bottleneck for the large-scale implementation of ligno-
liquid fuels must address one important limitation of this cellulose-derived biofuel industry.36
resource: the low energy-density of biomass compared to fossil Recalcitrance of lignocellulosic biomass can be explained in
fuels. Although the energy-density of biomass varies terms of its chemical structure, comprised of three major units:
considerably depending on the source, an average value for cellulose, hemicellulose and lignin.13,37,38 Cellulose (40–50%) is
biomass (15–20 MJ kg1) is well below that of crude oil a high molecular weight polymer of glucose units connected
(42 MJ kg1).30 Large amounts of biomass will thus be required linearly via b-1,4-glycoside linkages. This arrangement allows for
to produce liquid fuels, leading to high costs for transporting extensive hydrogen bonding between cellulose chains, which
the biomass source to the processing location.31 Furthermore, if confers this material with rigid crystallinity and, thus, high
biomass transportation involves utilization of fossil fuels, then resistance to deconstruction.39 Cellulose bundles are additionally
the overall CO2 emission savings of the bioprocess would be attached together by hemicellulose (15–20%), an amorphous
penalized. Consequently, for biomass conversion technologies (and consequently more readily deconstructed) polymer of five
to be cost-competitive and truly carbon-neutral, it is necessary different C5 and C6 sugars. Cellulose and hemicellulose, the
to develop efficient processing units at small scale that can be carbohydrate fraction of lignocellulose, are protected by
distributed close to the biomass source.17 Even though ethanol a surrounding three-dimensional polymer of propyl-phenol
plants achieve a significant size reduction compared to petro- called lignin (15–25%), which provides extra rigidity to the
chemical refineries, the mild conditions employed and the low lignocellulose structure. To overcome lignocellulose recalci-
levels of ethanol achieved for bacterial fermentation (e.g., trance, a variety of physical and chemical methods have been
30–50 C, ethanol concentrations lower than 15% v/v) signifi- developed, and a comprehensive description of such technologies
cantly limit the reaction rates and require reactors with a size can be found elsewhere.40–42 The approach most commonly used
large enough to make the process economically feasible. As will involves pretreatment of lignocellulose (with the aim of breaking/
be described in following sections, biomass-based hydrocarbon weakening the lignin protection and increasing the susceptibility
fuels, in contrast, can be produced at high temperatures and of crystalline cellulose to degradation), followed by hydrolysis to
using concentrated water solutions,14 which allow for faster depolymerize hemicellulose and cellulose and, thus, isolate the
conversions in smaller reactors. sugars from the lignin fraction.
The utilization of edible biomass (such as corn or cane sugar)
for the large-scale production of fuels can produce competition
3. Routes for the production of biofuels from biomass
with food for land use. The so-called food-versus-fuel debate has
arisen in many countries as a response to the sharp increase in The main pathways for the production of liquid transportation
food prices during 2007 and 2008. Although it has been pointed fuels from biomass are shown in Fig. 4. As indicated in previous
out that this rise in price was the result of several linked world- sections, food crops such as corn grain or sugar cane can be
wide events,22 some authors indicate that the increased demand converted into ethanol by fermentation processes. Alternatively,
for corn to produce ethanol had a direct impact on food prices, second generation ethanol can be produced from lignocellulosic
especially in food-insecure areas of the world where food is based sources by means of pretreatment–hydrolysis and subsequent
on grain consumption.32 These issues have driven researchers fermentation of soluble sugars. Butanol, with energy density and
around the world to develop technologies to process non-edible polarity similar to gasoline, can be also produced by this route,
biomass (e.g., lignocellulosic biomass), thereby permitting representing an interesting alternative to overcome many of the
sustainable production of a new generation of biofuels (so-called technical shortcomings of ethanol as a fuel.43,44 Interestingly, the
second generation of fuels), without affecting food supplies. microorganisms utilized for fermentation can be engineered to
Lignocellulosic biomass has two important advantages over convert sugars to liquid alkanes instead of alcohols.45 This new
edible biomass feedstocks: it is more abundant and can be grown technology could achieve improvements over classical fermen-
faster and with lower costs.33 In this respect, it is estimated that tation approaches, because hydrocarbons separate spontane-
the US could sustainably produce more than 1 billion tons of ously from the aqueous phase, thereby avoiding poisoning of
non-edible biomass per year by 2050 with relatively modest microbes by the accumulated products and facilitating separa-
changes in land use and agricultural and forestry practices. Once tion/collection of alkanes from the reaction medium.
converted into biofuels, these lignocellulosic resources would Vegetable oils, obtained from food sources such as soybeans,
have the potential to displace more than one third of the petro- palm or sunflower, can serve as feedstocks for the production of
leum currently consumed by the transportation sector.34 Ligno- first-generation biodiesel through transesterification processes.
cellulosic feedstocks ($3 per GJ) are slightly less expensive than Since vegetable oils are expensive and compete with food sour-
edible biomass (5$ per GJ), and potentially more economical ces, the challenge of the biodiesel industry is to find non-edible
than crude oil (10–15 $ per GJ) and vegetable oils (18–20 $ per sources of lipids. Algae crops are receiving interest in this
GJ); however, due to its recalcitrant nature, lignocellulose is respect,46 although the high cost associated with feedstock
more difficult to convert and, consequently, processing costs production is an important barrier, and related technologies are
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Fig. 4 Routes for the conversion of biomass into liquid fuels. Red arrows refer to thermal routes, green arrows refer to biological routes, and blue
arrows refer to catalytic routes. Adapted from ref. 25.
presently at an early stage of development. Green diesel can be hydrocarbon fuels. Thus, gasification converts solid biomass to
produced from plant oils and animal fats by means of deoxy- synthesis gas (syngas), a valuable mixture of CO and H2 which
genation reactions under hydrogen pressure in hydrotreating serves as a precursor of liquid hydrocarbon fuels by Fischer–
processes.47,48 This recent technology has potential in that it can Tropsch (F–T) reactions. This pathway is commonly known as
be carried out in existing petroleum refinery infrastructure.49 biomass to liquids (BTL). Pyrolysis allows transformation of
Representative examples of non-food lignocellulosic feed- lignocellulosic biomass into a liquid fraction known as bio-oil
stocks such as forest wastes, agricultural residues like corn that can be subsequently upgraded to hydrocarbon fuels by
stover, or municipal paper wastes are shown in Fig. 4. Apart a variety of catalytic processes. The third route involves
from their intrinsic recalcitrance, these feedstocks are charac- pretreatment–hydrolysis steps to yield aqueous solutions of C5
terized by a high degree of chemical and structural complexity, and C6 sugars derived from lignocellulose. While gasification and
and, consequently, technologies for the conversion of these pyrolysis are pure thermal routes in which lignocellulose is
resources into liquid hydrocarbon fuels typically involve decomposed with temperature under controlled atmosphere,
a combination of different processes. The methodology most aqueous-phase processing, in contrast, involves a series of cata-
commonly used to overcome lignocellulose complexity involves lytic reactions to selectively convert sugars and important plat-
the transformation of non-edible feedstocks into simpler frac- form chemicals derived from them into targeted liquid
tions that are subsequently more easily converted into a variety hydrocarbon fuels with molecular weights and structures
of useful products. This approach, similar to that used in appropriate for gasoline, diesel and jet fuel applications.
conventional petroleum refineries, would allow the simultaneous
production of fuels, power, and chemicals from lignocellulose in
an integrated facility denoted as a biorefinery.50,51 Current tech- 4. Production of liquid hydrocarbon transportation
nologies for converting lignocellulose to liquid hydrocarbon fuels from lignocellulose
transportation fuels involve three major routes: gasification,
4.1 Biomass to liquids (BTL)
pyrolysis and pretreatment–hydrolysis (Fig. 4). By means of
these primary routes, lignocellulose is converted into gaseous and Biomass to liquids can be described as a renewable version of
liquid fractions that are subsequently upgraded to liquid fossil fuel-based technologies like coal to liquids (CTL) and gas
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to liquids (GTL), involving the integration of two different positive aspect of BTL is its versatility. Thus, since any source of
processes: biomass gasification to syngas (H2/CO) and F–T lignocellulose can be potentially gasified, BTL technologies are
synthesis. Even though both technologies are well known and not constrained to a particular biomass feedstock or fraction.
relatively mature, integration remains a challenge in BTL,
because the utilization of lignocellulosic biomass as a feedstock
4.2 Pyrolysis integrated with upgrading processes
(in substitution for classical carbon sources such as coal and
natural gas) introduces new difficulties in the overall process. Lignocellulosic biomass can be treated under inert atmosphere at
Biomass gasification is achieved by treatment at high tempera- temperatures of 648–800 K in a process called pyrolysis. At these
tures (e.g., 1100–1500 K) under a well-controlled oxidizing conditions, solid biomass undergoes a number of processes
atmosphere (e.g., air, steam, oxygen). Control over the compo- including depolymerization, dehydration and C–C bond
sition of the outlet gaseous stream is difficult and depends on breaking reactions which lead to the formation of reactive vapor
a variety of factors including the oxidizing agent, biomass species.35 Upon subsequent cooling, the vapor products condense
particle size and gasifier design.52 In this respect, research indi- generating a dark viscous liquid referred to as bio-oil. This bio-
cates that utilization of pure oxygen atmosphere, small particle oil is a complex mixture of more than 400 highly oxygenated
sizes (lower than 1 mm diameter), and a combination of high compounds, including acids, alcohols, aldehydes, esters, ketones
temperatures, high pressures and low residence times favors the and aromatic species, along with some remnants of polymeric
production of syngas versus producer gas (a mixture of CO, H2, carbohydrates and lignin fragments.63,64 Consequently, once
CO2, CH4, and N2 used for heat and electricity production).53–55 separated into their components, bio-oil could serve as a source
The direct integration of biomass gasification and F–T of chemicals. The final composition of the bio-oil depends on
synthesis requires an intermediate gas-cleaning system, because a large number of factors (e.g., feedstock type, reaction condi-
the gaseous stream delivered from the gasifier typically contains tions, alkali content of the feedstock, storage conditions). Bio-
a number of contaminants that need to be removed before the oils typically contain about 25 wt% water (derived from the
F–T unit, which is highly sensitive to impurities. Thus, tars initial water of the feedstock and from the pyrolysis process
(condensable high molecular weight hydrocarbons produced by itself), and retain up to 70% of the energy stored in the biomass
incomplete biomass gasification), volatile species such as NH3, feedstock,52 thereby allowing for concentration of the energy of
HCl, and sulfur compounds (produced by gasification of ligno- biomass in a dense liquid that is more easily transportable. The
cellulose impurity components), fine particles, and ashes typi- main advantage of pyrolysis over BTL is its simplicity, because it
cally accompany CO and H2 in the outlet gaseous stream. The requires only a single reactor and low capital investments,
high number of contaminants, along with the strict cleaning thereby allowing the development of cost-effective processing
standards imposed by the F–T unit,56 require the use of multiple units on small scale. Thus, small portable pyrolysis reactors (i.e.,
steps and advanced technologies52 that contribute significantly to 50–100 tons of biomass per day) are currently commercially
the complexity and cost of the BTL plant. Additionally, because developed to produce liquid biofuels close to the biomass loca-
biomass contains higher amounts of oxygen compared to coal, tion in countries like the US, Canada and the Netherlands.65,66
the syngas delivered from lignocellulosic sources is typically Even though bio-oils can be used directly in simple boilers and
enriched in CO (H2/CO ¼ 0.5), and F–T synthesis requires turbines for heat and electricity production, their utilization as
syngas with a H2/CO ratio closer to 2.57,58 By providing sufficient transportation fuels has multiple shortcomings. The high oxygen
water co-feeding, the H2/CO ratio can be adjusted by means of an content of bio-oils negatively affects the energy density (16–19
intermediate water gas-shift (WGS, CO + H2O / CO2 + H2) MJ kg1 versus 46 MJ kg1 of regular gasoline), and it leads to
reactor situated between the gasifier and the F–T unit. low volatility and poor stability properties of the bio-oil liquid.
The F–T reactor, the last unit of the BTL plant, achieves Furthermore, the high corrosiveness (pH z 2.5) and viscosity of
conversion of syngas to a distribution of alkanes over Co-, Fe-, bio-oils discourage their utilization in internal combustion
or Ru-based catalysts in a well-developed industrial process.58 engines. Since the pyrolysis process does not involve a deep
However, the hydrocarbons produced by the direct route range chemical transformation in the feedstock, extensive oxygen
from C1 to C50, and neither gasoline nor diesel fuels can be removal is required for bio-oils to have hydrocarbon-like prop-
produced selectively without generating a large amount of erties (e.g., high energy density, high volatility and high thermal
undesired products. Indirect approaches involve initial produc- stability), and several routes are available in this respect (Fig. 5).
tion of heavy hydrocarbons (waxes), followed by controlled Hydrodeoxygenation (i.e., treatment of the bio-oil at moderate
cracking of the heavy compounds to diesel and gasoline temperatures and high hydrogen pressures, HDO) is probably
components to overcome this limitation.59 the most common method to achieve oxygen removal from bio-
The cost of producing the biofuel, negatively affected by the oils.67,68 By means of this technology, bio-oil components are
complexity of the process, is the main factor limiting the completely hydrogenated and oxygen is removed in the form of
commercialization of BTL technologies. Application of econo- water, which appears in the reactor as a separate phase from the
mies-of-scale allows for improvements in the economics of the hydrocarbon layer. Hydrodeoxygenation is typically carried out
process at the expense of having large centralized facilities that, over sulfided CoMo and NiMo based catalysts68 (used in the
as indicated in a previous section, lead to higher costs for petrochemical industry to achieve sulfur and nitrogen removal
transporting the low energy density biomass. BTL profit margins from crude oil). Precious metals such as Pt and Ru69,70 show
can be increased by co-producing, along with liquid hydrocarbon higher hydrogenation activities at the expense of low tolerance to
fuels, higher-value chemicals such as methanol60 and sulfur impurities (typically present in bio-oils). The large amount
hydrogen61,62 from lignocellulose-derived syngas. Another of hydrogen required for bio-oil deoxygenation represents the
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downstream processes is catalytic ketonic decarboxylation or

ketonization80 (Fig. 5). By means of this reaction, 2 molecules of
carboxylic acids are condensed into a larger ketone (2n 1
carbon atoms) with the release of stoichiometric amounts of CO2
and water. This reaction is typically catalyzed by inorganic
oxides such as CeO2, TiO2, Al2O3 and ZrO2 at moderate
temperatures (573–698 K) and atmospheric pressure.81–84 Inter-
estingly, ketonization achieves oxygen removal (in the form of
water and CO2) while consuming carboxylic acids, the latter of
which represent an important fraction of bio-oils (up to
30 wt%).85 Moreover, these acids are hydrogen-consuming
compounds, and are responsible for unwanted properties of the
bio-liquids such as corrosiveness and chemical instability.

Consequently, as represented in Fig. 5, a pretreatment of the bio-
oil over a ketonization bed would simultaneously reduce oxygen
content and acidity, thereby reducing hydrogen consumption
and leaving bio-oil more amenable for subsequent hydro-
deoxygenation processing. Even though ketonization has not
Fig. 5 Catalytic routes for the upgrading of biomass-derived oils into
been used to process real lignocellulosic bio-oils so far, we believe
liquid hydrocarbon transportation fuels.
that this route has potential to upgrade bio-liquids enriched in
carboxylic acids. Furthermore, ketonization can also condense
main drawback of this technology,71 and strategies based on typical components of bio-oils like esters,86–88 and, unlike zeolite
steam-reforming of the water-soluble fraction of bio-oils,72 along upgrading, this reaction can be efficiently carried out under
with aqueous-phase reforming of biomass-derived sugars,73,74 moderate amounts of water.89
have been studied to avoid the need to supply hydrogen from
external fossil fuel sources. Bio-oils typically contain significant
4.3 Aqueous-phase processing of biomass derivatives
amounts of lignin-derived phenols which, once transformed into
aromatic hydrocarbons, are valuable gasoline components.75 As indicated in Fig. 4, aqueous solutions of sugars, derived from
One of the challenges of the hydrodeoxygenation process is to the carbohydrate fraction of lignocellulose (i.e., cellulose and
achieve complete hydrogenation of aliphatic compounds while hemicellulose), can be used to produce second generation ethanol
avoiding unnecessary hydrogen consumption in the reduction of fuel through fermentation routes. Alternatively, these sugars can
the valuable aromatic hydrocarbons. However, this control over be transformed into a variety of useful derivatives by means of
the extent of the hydrogenation process is difficult at the elevated chemical and biological processes.90,91 As will be addressed in this
hydrogen pressures required for hydrodeoxygenation (e.g., section, sugars and some of their derivatives can be catalytically
100–200 bars). In addition, high pressures lead to increases in processed in the aqueous phase to produce liquid fuels chemically
operational costs of the process. identical to those currently used in the transportation sector. The
Bio-oil deoxygenation can be alternatively carried out at key advantage of this route, in comparison with BTL and
milder conditions (e.g., 623–773 K, atmospheric pressure) and pyrolysis-upgrading approaches, is derived from the mild reac-
without external hydrogen by processing the bio-liquid over tion conditions used, allowing for better control of conversion
acidic zeolites, in a route that resembles the catalytic cracking selectivity. However, costly pretreatment and hydrolysis steps are
approach used in petroleum refining.76–78 At these conditions, required to hydrolyze solid lignocellulose to soluble sugar feeds,
bio-oil components undergo a number of reactions involving and the lignin fraction, once isolated, is typically combusted to
dehydration, cracking and aromatization, and oxygen is provide heat and power.
removed in the form of CO, CO2 and water (Fig. 5). As a result, The production of liquid hydrocarbon transportation fuels
bio-oil is converted into a mixture of aliphatic and aromatic from biomass derivatives involves deep chemical trans-
hydrocarbons, although a large fraction of the organic carbon formations. In this respect, sugars (and chemicals derived from
reacts to form solid carbonaceous deposits denoted as coke. them) are molecules with high degrees of functionality (e.g.,
Thus, hydrocarbon yields are relatively modest and regeneration –OH, –C]O and –COOH groups) and a maximum number of
cycles under air (to burn off the coke) are frequent. Irreversible carbon atoms limited to six (derived from glucose monomers).
deactivation, caused by partial de-alumination of zeolite struc- On the other hand, hydrocarbon fuels are larger (up to C20 for
tures at the water contents typically found in bio-oils, is another diesel applications) and completely unfunctionalized
drawback of this technology, and research is needed on new compounds. Consequently, a number of reactions involving
acidic catalytic materials with better resistance to water.16 On the oxygen removal (e.g., dehydration, hydrogenation, and hydro-
other hand, the conditions of pressure and temperature at which genolysis), combined with C–C coupling (e.g., aldol condensa-
zeolite upgrading is carried out are similar to those used in tion, ketonization, and oligomerization), will be required to
pyrolysis, thereby allowing the integration of these two processes convert sugars into hydrocarbon transportation fuels, and
in a single reactor, as recently demonstrated by Huber et al.79 aqueous-phase catalytic processing offers the opportunity to
A third route that could help to reduce oxygen content in bio- selectively carry out those transformations. Importantly,
oils while leaving the bio-liquid more amenable for subsequent two aspects are crucial to ensure economic feasibility of the
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aqueous-phase route: (i) reduction of the number of processing 100 kg of glycerol per ton of biodiesel in the form of concentrated
steps by means of catalytic coupling approaches92 and (ii) aqueous solutions (80 wt%) are annually produced worldwide in
deoxygenation of biomass feedstocks with minimal consumption the biodiesel industry as a byproduct of the transesterification of
of hydrogen from an external source.93 vegetable oils and animal fats with methanol.98 The high number
The main aqueous-phase routes to upgrade sugars and deriv- of applications of glycerol in different fields such as cosmetics,
atives into liquid hydrocarbon transportation fuels are schemat- pharmaceuticals, foods, and drinks cannot absorb the surplus of
ically shown in Fig. 6. The biomass derivatives have been selected this compound created by the biodiesel industry. Extra glycerol
in view of their potential to produce liquid hydrocarbon fuels. could be consumed as a fuel in internal combustion engines but,
First, we will describe the catalytic route designed to convert unlike ethanol, glycerol cannot be used blended with gasoline
glycerol into liquid hydrocarbon fuels. This route involves the because of its low solubility in hydrocarbons and high viscosity.
integration of two processes: aqueous-phase reforming (APR) of Furthermore, the purification of crude aqueous glycerol for
glycerol to syngas and F–T synthesis. This approach is particu- chemical purposes is costly and energy-consuming. Conse-
larly interesting because glycerol is produced in large amounts as quently, new technologies, with potential to upgrade aqueous
a waste stream of the growing biodiesel industry.94 Furthermore, solutions of glycerol, would be valuable. In this respect,
glycerol can be co-produced, along with ethanol, by bacterial a promising route for glycerol conversion involves the produc-
fermentation of sugars95 (Fig. 4). Secondly, we will address tion of syngas through aqueous-phase reforming (APR)
furfural and hydroxymethylfurfural (HMF) as important processes.99 By means of this route, concentrated aqueous solu-
compounds obtained by chemical dehydration of biomass- tions of glycerol can be converted to gaseous H2, CO and CO2
derived sugars. Furfural and HMF can be used as platform mixtures over supported metal catalysts at moderate tempera-
chemicals for green diesel and jet fuel production through dehy- tures (498–548 K). Platinum is the preferred metal for this
dration, hydrogenation and aldol-condensation reactions. More conversion because it favors C–C cleavage reactions (leading to
recently, our group has developed a two-step (involving sugar CO, H2 and CO2) versus C–O cleavage reactions (leading to light
reforming/reduction and C–C coupling processes) cascade cata- hydrocarbons).73,100 To selectively produce syngas versus CO2-
lytic approach to convert aqueous solutions of sugars and polyols enriched mixtures, reaction conditions and catalytic materials
into the full range of liquid hydrocarbon fuels, and this process must be selected to control WGS reactions. Thus, by operating
will be described in Section 4.3.3. Finally, we will analyze the with inert materials like carbon as a support (instead of using
potential of two important biomass derivatives, levulinic acid inorganic oxide supports that can activate water), low total
(LA, obtained from sugars or HMF through dehydration pressures (to avoid high partial pressures of water), and high
processes) and g-valerolactone (GVL, obtained by hydrogenation glycerol concentrations (allowing water to become the limiting
of LA), to produce liquid hydrocarbon fuels. reagent in WGS), syngas streams with adequate H2/CO ratios for
Fischer–Tropsch synthesis can be produced from aqueous
4.3.1 Glycerol conversion to liquid hydrocarbon fuels. Glyc- glycerol over Pt/C catalysts.99
erol (1,2,3-propanetriol) is a water-soluble biomass-derived To allow for coupling of endothermic glycerol reforming with
polyol with versatile chemical reactivity.94,96,97 Approximately exothermic Fischer–Tropsch synthesis in a single reactor, it is
Fig. 6 Main catalytic routes for the aqueous-phase conversion of sugars and derivatives into liquid hydrocarbon transportation fuels.
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crucial that the former process is carried out efficiently at low condensations are base-catalyzed (e.g., NaOH, Mg–Al oxides)
temperatures. However, under these conditions, the metallic and are typically carried out in polar solvents like water. As
surface of Pt is likely to be saturated with adsorbed CO,101 thus a result of the aldol-condensation, a larger compound containing
decreasing the overall catalytic rate. One effective strategy to unsaturated C]C and C]O bonds (i.e., aldol-adduct) is formed
overcome this limitation involves the utilization of alloys such as and, owing to its hydrophobic character, this adduct precipitates
Pt–Re and Pt–Ru, on which the strength of adsorption of out of the aqueous solution. Recently, improvements have been
CO is lower compared to Pt.102,103 This new route involving made in the aldol-condensation process by utilizing biphasic
low-temperature gasification of aqueous glycerol to syngas reactors where furan compounds (dissolved in organic THF) are
integrated with Fischer–Tropsch synthesis represents an inter- contacted with aqueous NaOH, thus allowing continuous
esting alternative to complex BTL approaches (Section 4.1). extraction of aldol-adducts into the organic phase.110 As repre-
Thus, unlike biomass gasification, glycerol reforming can be sented in Fig. 7, the molecular weight of final alkanes can be
carried out at temperatures within the range employed for increased by allowing adducts to undergo a second aldol-
Fischer–Tropsch synthesis, thereby allowing effective integration condensation process with the initial furanic feedstock. The
of both processes in a single reactor104 with improved thermal unsaturated C]C and C]O bonds in aldol adducts are subse-
efficiency (since heat required for endothermic reforming is quently hydrogenated over metal catalysts such as Pd to yield
provided by exothermic F–T process). Furthermore, concen- large water-soluble polyol compounds. The complexity of the
trated aqueous solutions of glycerol (as produced in biodiesel process can be reduced by using a bifunctional (metal and basic
facilities) can be converted to undiluted and impurity-free sites) water-stable Pd/MgO–ZrO2 catalyst.113 Thus, both aldol-
syngas, thereby eliminating the need for large gasifiers with condensation and adduct hydrogenation can be carried out
oxygen-production plants and expensive gas-cleaning units. simultaneously in a single reactor. The last step of the process
Thus, unlike BTL, this aqueous-phase route allows for cost- involves complete oxygen removal from the hydrogenated aldol-
competitive operations at small scale, which is advantageous for adducts to produce liquid alkanes through aqueous-phase
the processing of distributed biomass resources. dehydration/hydrogenation (APD/H) reactions.114 Oxygen is

progressively removed from the water-soluble adducts over
4.3.2 HMF and furfural platforms to hydrocarbon fuels. a bifunctional metal–acid catalyst by cycles of dehydration and
Furan compounds such as furfural (2-furaldehyde) and HMF are hydrogenation reactions. APD/H can be achieved over Pt–SiO2–
obtained by dehydration of sugars over mineral acid catalysts Al2O3 in a four-phase reactor involving aqueous solution of
such as HCl or H2SO4 at moderate temperatures (e.g., 423 K). adducts, a hydrogen gas inlet stream, a hexadecane sweep
These furan compounds find applications as chemical interme- stream, and the solid catalyst.109 The hexadecane stream is
diates in the production of industrial solvents, polymers and fuels important in that it prevents intermediate organic species from
additives. Furfural is obtained by dehydration of C5 sugars like overreacting to coke over acid sites. Recently, the utilization of
xylose in a well-developed industrial process.105 On the other a bifunctional Pt/NbPO4 catalyst, with superior dehydration
hand, the large-scale production of HMF from C6 sugars is more activity under water environments,115 has allowed elimination of
complicated, and several aspects still remain a challenge, one of the hexadecane sweep stream step and, consequently, production
which is the utilization of glucose as a sugar feedstock. Thus, of a pure organic stream of liquid hydrocarbon fuels with tar-
HMF is typically produced from glucose with low yields, and geted molecular weights (C9–C15 for HMF and C8–C13 for
current technologies include an additional isomerization step to furfural) that spontaneously separates from water and retains
fructose, since dehydration of fructose to HMF takes place with 60% of the carbon of the initial sugar feedstock.110
better selectivity and higher rates.106,107 Furthermore, the control
over the unwanted side reactions involving the reactant, inter- 4.3.3 Reforming/reduction of sugars. The catalytic trans-
mediates and the final HMF product is critical. It is particularly formation of sugars to liquid hydrocarbon fuels is a complicated
important to prevent HMF from overreacting in the aqueous process that ideally should combine deep oxygen removal and
phase, and utilization of biphasic reactors where HMF is adjustment of the molecular weight using a small number of
continuously extracted into an organic solvent has shown reactors and with minimal utilization of fossil fuel-based external
promising results.108 hydrogen. This goal can be achieved by (i) using multifunctional
Furfural and HMF can be used as building blocks for the catalysts able to carry out different reactions in the same
production of linear hydrocarbons (in the molecular weight reactor92 and (ii) utilizing a fraction of the sugar feedstock as
appropriate for diesel and jet fuel) by means of a cascade process a source of in situ hydrogen through aqueous-phase reforming
involving dehydration, hydrogenation and aldol-condensation reactions.73
reactions,109,110 as shown in Fig. 7 for HMF. The process starts Both approaches are combined by Kunkes et al. in a recent
with acid-catalyzed deconstruction of polysaccharides (e.g., process that transforms aqueous solutions of sugars and sugar-
starch, cellulose or hemicellulose) to yield C5 and C6 sugar alcohols into liquid hydrocarbon fuels in a two-step cascade
monomers, which are subsequently dehydrated (under the same process116 (Fig. 8). Firstly, aqueous sugars and polyols (typically
acid environment) to form carbonyl-containing furan glucose and sorbitol) are converted into a mixture of mono-
compounds such as furfural and HMF. In a further step, the functional compounds (e.g., acids, alcohols, ketones and
carbonyl group in the furan compounds serves as a reactive heterocycles) in the C4–C6 range, which are stored in an organic
center for C–C coupling through aldol condensation reactions phase that spontaneously separates from water. This step is
with carbonyl-containing molecules such as acetone, which can carried out at temperatures near 500 K over a Pt–Re/C catalyst,
be also obtained from biomass-derived sources.111,112 These which achieves deep deoxygenation (up to 80% of the oxygen in
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Fig. 7 Reaction pathways for the conversion of biomass-derived glucose into liquid alkanes via HMF. Adapted from ref. 109.
the initial feedstock is removed) by means of C–O hydrogenolysis removal of acids by ketonization (similar to those proposed
reactions. Importantly, the hydrogen required to accomplish the herein for bio-oils upgrading, Section 4.2) and subsequent aldol-
C–O cleavage step is internally supplied by aqueous-phase condensation have been successfully developed.120–122 Ketoniza-
reforming (involving C–C cleavage and WGS reactions) of tion acquires special relevance when the organic stream is rich in
a fraction of the feed (Fig. 8). The Pt–Re/C material allows carboxylic acids, as is the case when the feed is glucose.
production of hydrogen and removal of oxygen in a single
reactor. Unlike bio-oils produced by pyrolysis (Section 4.2), the 4.3.4 Levulinic acid and g-valerolactone platforms to hydro-
organic stream of monofunctional compounds produced by carbon fuels. Levulinic acid (4-oxopentanoic acid) is an impor-
sugar processing over Pt–Re/C is completely free of water and tant biomass derivative that can be obtained by acid hydrolysis
has a well-defined composition that is controlled by the feedstock of lignocellulosic wastes, such as paper mill sludge, urban waste
type (e.g., sugars or polyols) and the reaction conditions.117 paper, and agricultural residues, through the Biofine process.123
The retention of functionality in the organic intermediates is Levulinic acid has been recently selected by the US Department
key to control reactivity and to allow subsequent C–C coupling of Energy (DOE) as one of the top 15 carbohydrate-derived
upgrading strategies. This approach has been demonstrated to be chemicals in view of its potential to serve as a building block for
conceptually adequate to process sugars into fuels,3 and impor- the development of biorefinery processes.91 Thus, taking
tant biomass derivatives such as lactic acid (3-hydroxypropanoic advantage of its dual functionality (i.e., a ketone and an acid
acid)89,118 and levulinic acid119 have been upgraded following this group), a number of useful chemicals can be synthesized from
strategy. Each group of compounds (e.g., alcohols, ketones, levulinic acid including methyltetrahydrofuran (MTHF) (a
acids) in the monofunctional stream can be upgraded to targeted gasoline additive) and d-aminolevulinic acid (DALA) (a biode-
hydrocarbons through different C–C coupling reactions (e.g., gradable pesticide).124
oligomerization, aldol-condensation and ketonization). For Recently, our group has developed a series of catalytic
example, the organic stream enriched in alcohols by hydroge- approaches to convert aqueous solutions of levulinic acid into
nation of ketones can be processed over an acidic H-ZSM5 liquid hydrocarbon transportation fuels of different classes
zeolite at atmospheric pressure to yield 40% of C6+ aromatic (Fig. 9). The catalytic pathways involve oxygen removal by
gasoline components. Ketones can be upgraded to larger dehydration/hydrogenation (in the form of water) and decar-
hydrocarbon compounds (C8–C12) with low extents of branching boxylation (in the form of CO2) reactions, combined with C–C
by means of aldol-condensation reactions over bifunctional Cu/ coupling processes such as ketonization, isomerization, and
Mg10Al7Ox catalysts. However, carboxylic acids present in the oligomerization that are required to increase the molecular
organic stream caused deactivation of the basic sites responsible weight and to adjust the structure of the final hydrocarbon
for aldol-condensation, and approaches based on upstream product. As a first step, aqueous levulinic acid is hydrogenated
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Fig. 8 Scheme of the process for the catalytic conversion of sugars and polyols into liquid hydrocarbon fuels. Sugars primarily undergo reforming/
reduction over Pt–Re/C to generate intermediate hydrophobic monofunctionals. The intermediates can be upgraded to liquid hydrocarbon fuels by
means of C–C coupling reactions. Adapted from ref. 116.
to water-soluble GVL, which is the key intermediate for the a maximum of 70% carbon yield.119 Nonanone yield can be
production of hydrocarbon fuels. This hydrogenation step can increased to almost 90% by using a dual-catalyst approach with
be achieved with high yields by operating at low temperatures Pd/Nb2O5 + Ce0.5Zr0.5O2 in a reactor with two different temper-
(e.g., 423 K) over non-acidic catalysts (e.g., Ru/C) to avoid ature zones, which allows for optimum control of reactivity.131 5-
formation of angelica lactone, a known coke precursor125 Nonanone, which is obtained in a high purity organic stream that
which is produced by dehydration over acidic sites at higher spontaneously separates from water, is subsequently transformed
temperatures (e.g., 573–623 K).119 Interestingly, because equi- into its corresponding alcohol that serves as a platform molecule
molar amounts of formic acid (a hydrogen donor) are co- for the production of hydrocarbon fuels for gasoline and diesel
produced along with levulinic acid in the C6-sugars dehydra- applications. For example, the C9 alcohol can be processed
tion process, this hydrogenation step could be potentially (through hydrogenation/dehydration cycles) over a bifunctional
carried out without utilizing hydrogen from an external source, metal–acid catalyst such as Pt/Nb2O5110 into linear n-nonane, with
and several groups have already explored this possibility.126,127 excellent cetane number and lubricity to be used as a diesel blender
This route is promising in that GVL has applications as agent. Alternatively, the functionality of 5-nonanol can be utilized
a gasoline additive,128 and as a precursor to polymers129 and to upgrade the alcohol to gasoline and diesel components. In
fine chemicals.130 particular, 5-nonanol can be dehydrated and isomerized in
Aqueous solutions of GVL can be upgraded to liquid hydro- a single step over an USY zeolite catalyst to produce a mixture of
carbon fuels by following two main pathways: the C9 route and branched C9 alkenes with the appropriate molecular weight and
the C4 route (Fig. 9). In the former route, GVL is converted to structure for use in gasoline after hydrogenation to the corre-
5-nonanone over a water-stable multifunctional Pd/Nb2O5 cata- sponding alkanes.131 Additionally, 5-nonanol can be converted
lyst. In this process, GVL is first transformed into hydrophobic into a C9-alkene stream (by means of dehydration reactions)
pentanoic acid by means of ring-opening (on acid sites) and which can be subsequently oligomerized over an acid catalyst such
hydrogenation reactions (on metal sites) at moderate tempera- as Amberlyst 70 to achieve good yields of C18 alkanes (after
tures and pressures. Pentanoic acid is subsequently ketonized to 5- hydrogenation) for diesel applications.132
nonanone, and reaction conditions can be adjusted to allow this Recently, a promising route to upgrade aqueous solutions
transformation to take place on the same Pd/Nb2O5 reactor with of GVL into jet fuels through the formation of C4 alkenes has
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Fig. 9 Catalytic routes for the conversion of levulinic acid (LA) and g-valerolactone (GVL) into liquid hydrocarbon transportation fuels. Blue colour
indicates water-soluble compounds, yellow symbolizes hydrophobic compounds, and green refers to liquid hydrocarbon fuels.
been developed by Bond et al.133 (Fig. 9). The process is based 5. Comparison of technologies for biomass
on a dual reactor system. In the first catalytic reactor the conversion into liquid hydrocarbon fuels
GVL feed undergoes decarboxylation at elevated pressures
(e.g., 36 bars) over a silica/alumina catalyst, producing a gas Table 1 summarizes the main characteristics of the different
stream composed of butene isomers and CO2. In a second technologies analyzed in the present perspective paper for the
reactor connected in series, the gaseous butene stream is conversion of biomass into liquid hydrocarbon fuels. Various
passed over an acidic catalyst (H-ZSM5, Amberlyst 70) that routes have been compared in terms of important parameters
achieves oligomerization of butene monomers, yielding (e.g., pretreatment required, external chemicals and hydrogen
a distribution of alkenes centred at C12. While CO2 does not requirements, reaction conditions, cleaning/separation steps,
affect the oligomerization process other than by dilution, number of reactors, use of precious metal catalysts) involved in
water inhibits the acidic oligomerization catalyst (especially the processing from the initial lignocellulosic biomass to the final
Amberlyst), and it has to be removed prior to the second liquid hydrocarbon fuel. Additionally, technologies are
reactor by using a gas–liquid separator operating at 36 bars compared in terms of the overall yield of LHF for each route,
and 373–398 K. The final optimized yield to C8+ alkenes calculated according to recent data available in literature. The
reaches 75% when silica/alumina and Amberlyst 70 are used. ability to use the entire organic matter in lignocellulose repre-
Since GVL can be potentially produced from levulinic acid sents the main advantage of thermal routes (i.e., BTL and
with no external hydrogen requirements, this technology pyrolysis + upgrading) versus aqueous-phase approaches which,
allows the production of liquid hydrocarbon alkanes from as indicated in Section 4.3, only can process the sugar fraction of
lignocellulose with minimal utilization of hydrogen (i.e., lignocellulose (typically 60–80% depending on the source13). This
hydrogen is only used during the final alkene hydrogenation constraint in aqueous-phase routes has important consequences
step). Furthermore, the process is potentially cost-competitive for the overall process: (i) it limits the final yield to LHF and (ii) it
with petroleum-derived technologies, since only two reactors negatively affects the economics since additional reactors for
are required, operating in series and using non-precious metal- pretreatment/hydrolysis steps are required to solubilize the sugar
catalysts. Finally, a CO2 gas stream is produced with high feedstocks (Table 1). On the other hand, aqueous-phase
purity and at high pressures, thereby permitting effective processes are carried out at milder conditions compared to
utilization of sequestration or capture technologies to mitigate thermal routes which allows for better control of the chemistry
greenhouse gas emissions. and, with it, higher selectivities to targeted hydrocarbon fuels.
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Table 1 Summary of the different technologies for the conversion of biomass into liquid hydrocarbon transportation fuels
Technology
Thermal routes Aqueous-phase routes
GVL platform
Glycerol Reforming of
BTL Pyrolysis reforming HMF platform sugars C9 route C4 route
Use of entire Yes Yes No No No No No

lignocellulose
Pretreatment Drying, size Drying, size Oil extraction Pretreatment Pretreatment, Pretreatment Pretreatment
required reduction reduction [acid hydrolysis [acid [acid
hydrolysis hydrolysis hydrolysis
a a
dehydration] , dehydration] , dehydration]a,
isomerization hydrogenation hydrogenation
External Oxygen Inert gas Methanol Acetone, mineral Enzymes/mineral Mineral acid Mineral acid
chemicals acid, acid
required extracting
solvent
Reaction 1100–1500 K, 650–800 K, 498–548 K, 298–393 K, 483–523 K, 598–698 K, 443–648 K,

conditions 1–20 bar 1 bar 1–20 bar 1–55 bar 18–27 bar 14–35 bar 36 bar
Intermediate Syngas Bio-oil Syngas Hydrogenated Monofunctionals 5-Nonanone- Butene + CO2

fraction aldol-adduct organic stream enriched

organic phase
Cleaning/ Deep cleaning, Char removal Not required Extraction with Not required Not required Water removal
conditioning/ WGS organic (spontaneous (spontaneous
separation solvent separation) separation)
Upgrading F–T HDO or zeolite F–T APD/H C–C coupling, Hydrogenation, Oligomerization,
process upgrading dehydration, C–C coupling, hydrogenation
hydrogenation dehydration
Number of 2–3b 2 2 4 4 5–7c 4

reactors
Precious metal No Yes Yes Yes Yes Yes No

catalysts
involved
External H2 No High with HDO, No Moderate No Moderate Minimum

requirements none with
zeolite
LHF yield (g fuel 0.21d 0.45–0.15e 0.011f 0.27–0.10g 0.23–0.16h 0.25–0.19i 0.25–0.19j
per g dry
biomass)
a
[ ] indicates that hydrolysis and dehydration can be carried out in the same reactor. b 3 reactors if WGS syngas conditioning is required. c Depending on
the upgrading process required. d According to ref. 134. e Calculated as: [0.50–0.70 yield of bio-oil from lignocellulose in pyrolysis135] [0.65 yield of
LHF in HDO,136 or 0.30 yield of aromatics LHF in zeolite upgrading79]. f Calculated as: [0.20 content of oil in soybeans137] [0.1 glycerol in biodiesel
process] [0.552 yield of alkanes104]. g Calculated as: [0.80–0.60 sugar content of lignocellulose] [0.96 yield of hydrolysis enzymatic] [0.53–0.31 yield
isomerization glucose to fructose138,139] [0.69–0.58 yield of LHF from fructose110]. h Calculated as: [0.80–0.60 sugar content of lignocellulose] [0.96
yield of hydrolysis enzymatic] [0.52 yield of organic C116] [0.57 yield of C7+ ketones116]. i Yield to n-nonane (diesel blender). Calculated as: [0.80–0.60
sugar content of lignocellulose] [0.96 yield of hydrolysis enzymatic] [0.45 yield to levulinic acid of biofine process] [0.96 yield of levulinic acid to
GVL119] [0.80 yield of 5-nonanone from GVL119] [1.00] hydrogenation of 5-nonanone to n-nonane. j Calculated as: [0.80–0.60 sugar content of
lignocellulose] [0.96 yield of hydrolysis enzymatic] [0.45 yield to levulinic acid of biofine process] [0.96 yield of levulinic acid to GVL119]
[0.78 yield of C8+ alkenes133] [1.00] hydrogenation to final alkane product.
This control over the chemistry in aqueous phase technologies conditioning steps required. The higher number of reactors
has important implications on the cleaning/separation steps employed in the upgrading process for aqueous-phase routes
as well. Thus, unlike BTL and pyrolysis which produce inter- versus thermal routes is another important difference between
mediate fractions with high degrees of impurities that require both approaches. In some cases (for example reforming/reduc-
deep cleaning and conditioning before the upgrading process, tion of sugars, HMF and GVL platforms), the use of additional
aqueous-phase routes achieve high-purity organic streams that upgrading reactors is justified by the production of a final liquid
spontaneously separate from water, with no further cleaning/ hydrocarbon fuel with well-defined characteristics of molecular
View Online
weight and structure that could be directly used for gasoline, jet at the present time, suffers from low energy-density and
fuel and diesel applications (see Fig. 7–9). This control of the compatibility issues with the existing transportation infrastruc-
final hydrocarbon fuel is more difficult to achieve by BTL and ture, which is based on petroleum-derived liquid hydrocarbons.
pyrolysis, which produce a mixture of hydrocarbons with broad The current limitations of ethanol as a fuel can be overcome by
molecular weight distributions and low control of the final developing cost-effective technologies that allow conversion of
chemical structure. Consequently, thermal routes might need non-edible lignocellulosic biomass into liquid hydrocarbon fuels
additional refining reactors to produce fuel-grade compounds. chemically identical to those currently used in the transportation
As indicated in previous sections, two parameters are impor- sector. In this respect, several promising routes are currently
tant to assess the economic feasibility of aqueous-phase catalytic being developed worldwide, including gasification of biomass to
routes: the number of reactors and the use of external hydrogen. syngas coupled with F–T synthesis (BTL), pyrolysis integrated
Thus, glycerol reforming, with only 2 reactors (reforming and with bio-oils upgrading processes, and aqueous-phase catalytic
F–T) and no hydrogen requirements (Table 1), would represent processing of biomass-derived sugars and derivatives. BTL and
an interesting route. However, the final hydrocarbon yield pyrolysis-upgrading are thermochemical routes that allow utili-
(0.011 g of LHF per g of dry biomass), negatively affected by the zation of all the organic matter in lignocellulose, and aqueous-
low content of oils in the biomass source (20% in soybeans137), is phase processing is a catalytic route designed to operate with
low compared with other aqueous routes. With respect to these water-soluble sugars (and platform chemicals derived from
two parameters, reforming/reduction of sugars over Pt–Re is them). While aqueous-phase routes require that the lignocellu-
a promising route since no external hydrogen is required losic biomass be subjected to pretreatment/hydrolysis steps, these
(hydrogen required for reduction of sugars and hydrogenation of routes offer the opportunity to selectively carry out a variety of
the ketone formed by aldol-condensation or ketonization is reactions to achieve the deep chemical transformations and C–C
internally supplied in sufficient amounts by aqueous-phase coupling reactions required when converting sugars into liquid
reforming of a fraction of the sugar, Fig. 8), and only 4 reactors hydrocarbons. To be economically viable, these aqueous-phase
(hydrolysis, reforming, C–C coupling and dehydration/hydro- routes should be carried out with a small number of reactors and
genation) are needed to produce gasoline, diesel and jet fuel with minimum utilization of external fossil fuel-based hydrogen
components from lignocellulosic biomass with an overall yield sources, as illustrated in the examples presented in the present
comparable to that of BTL (0.21 g of LHF per g of dry biomass). paper.
The main drawback of this approach is the high cost of the Pt–Re
(10 wt%) reforming catalysts. The recently developed GVL
platform to produce butene oligomers offers an attractive alter- Acknowledgements
native with minimum external hydrogen utilization (required
only during the final alkene hydrogenation step) and no precious The results from the University of Wisconsin reported here were
metal catalysts, which should give this process a promising supported in part by the US Department of Energy Office of
economic assessment. The HMF platform route can achieve Basic Energy Sciences, by the DOE Great Lakes Bioenergy
good yields to LHF (with a maximum yield close to 0.3) at the Research Center (www.greatlakesbioenergy.org), and by the
expense of needing external chemicals such as acetone and Defense Advanced Research Project Agency.
organic solvents (typically produced from fossil fuels like
petroleum) and moderate amounts of hydrogen to carry out
APD/H. The GVL C9 route offers versatility to produce gasoline References
and C9–C27 diesel components with acceptable yields, but it
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Energy & Dynamic Article Links < C

1. Introduction millions of years to be formed, and they are currently being

Dr Juan Carlos Serrano-Ruiz James A. Dumesic earned his

Conventional transportation fuels are composed of liquid

portation liquids. Thus, instead of using biomass to produce

downstream processes is catalytic ketonic decarboxylation or

bio-liquids such as corrosiveness and chemical instability.

the processing of distributed biomass resources. dehydration/hydrogenation (APD/H) reactions.114 Oxygen is

Thermal routes Aqueous-phase routes

Use of entire Yes Yes No No No No No

Reaction 1100–1500 K, 650–800 K, 498–548 K, 298–393 K, 483–523 K, 598–698 K, 443–648 K,

Intermediate Syngas Bio-oil Syngas Hydrogenated Monofunctionals 5-Nonanone- Butene + CO2

fraction aldol-adduct organic stream enriched

Number of 2–3b 2 2 4 4 5–7c 4

Precious metal No Yes Yes Yes Yes Yes No

External H2 No High with HDO, No Moderate No Moderate Minimum

80 M. Renz, Eur. J. Org. Chem., 2005, 979. B, 2006, 66, 111.

86 R. Klimkiewicz, E. Fabisz, I. Morawski, H. Grabowska and 236.

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